6-- the zintl anion with the highest charge per atom obtained from solution

Christian B. Benda; Thomas F. Fässler

doi:10.1002/zaac.201300464

^6-- the zintl anion with the highest charge per atom obtained from solution

Christian B. Benda, Thomas F. Fässler

Chair of Inorganic Chemistry with Focus on New Materials

Technical University of Munich

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

From the dark-purple solution of the Zintl phase KBi in liquid ammonia dark-blue crystals of the ammonia solvate K₆[Bi₄](NH ₃)₈ were obtained. In contrast to known Bi_n polyanions the chemical bond in the anion [Bi₄]^6- is in accordance with the (8-N) rule featuring solely Bi-Bi single bonds. [Bi ₄]^6- is a butane-analog valence compound, and with 6 negative charges per 4 atoms it is the anion with the highest known charge per atom obtained from solution. The planarity of the trans-[Bi₄] ^6- unit hints at π orbital contributions of the bismuth atoms. The corresponding reactions of the phases K₅Bi₄ and K ₃Bi₂ in liquid ammonia in the presence of [2.2.2]crypt(4, 7, 13, 16, 21, 24-hexaoxa-1, 10-diazabicyclo-[8.8.8]hexacosane) lead to the salt [K([2.2.2]crypt)]₂[Bi₂](NH₃)₄ with the known electron-deficient [Bi₂]^2- polyanion and a Bi=Bi double bond.

Original language	English
Pages (from-to)	40-45
Number of pages	6
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	640
Issue number	1
DOIs	https://doi.org/10.1002/zaac.201300464
State	Published - Jan 2014

Keywords

Bismuth
Crystal structure
Zintl ion

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title = "6-- the zintl anion with the highest charge per atom obtained from solution",

abstract = "From the dark-purple solution of the Zintl phase KBi in liquid ammonia dark-blue crystals of the ammonia solvate K6[Bi4](NH 3)8 were obtained. In contrast to known Bin polyanions the chemical bond in the anion [Bi4]6- is in accordance with the (8-N) rule featuring solely Bi-Bi single bonds. [Bi 4]6- is a butane-analog valence compound, and with 6 negative charges per 4 atoms it is the anion with the highest known charge per atom obtained from solution. The planarity of the trans-[Bi4] 6- unit hints at π orbital contributions of the bismuth atoms. The corresponding reactions of the phases K5Bi4 and K 3Bi2 in liquid ammonia in the presence of [2.2.2]crypt(4, 7, 13, 16, 21, 24-hexaoxa-1, 10-diazabicyclo-[8.8.8]hexacosane) lead to the salt [K([2.2.2]crypt)]2[Bi2](NH3)4 with the known electron-deficient [Bi2]2- polyanion and a Bi=Bi double bond.",

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year = "2014",

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doi = "10.1002/zaac.201300464",

language = "English",

volume = "640",

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T1 - 6-- the zintl anion with the highest charge per atom obtained from solution

AU - Benda, Christian B.

AU - Fässler, Thomas F.

PY - 2014/1

Y1 - 2014/1

N2 - From the dark-purple solution of the Zintl phase KBi in liquid ammonia dark-blue crystals of the ammonia solvate K6[Bi4](NH 3)8 were obtained. In contrast to known Bin polyanions the chemical bond in the anion [Bi4]6- is in accordance with the (8-N) rule featuring solely Bi-Bi single bonds. [Bi 4]6- is a butane-analog valence compound, and with 6 negative charges per 4 atoms it is the anion with the highest known charge per atom obtained from solution. The planarity of the trans-[Bi4] 6- unit hints at π orbital contributions of the bismuth atoms. The corresponding reactions of the phases K5Bi4 and K 3Bi2 in liquid ammonia in the presence of [2.2.2]crypt(4, 7, 13, 16, 21, 24-hexaoxa-1, 10-diazabicyclo-[8.8.8]hexacosane) lead to the salt [K([2.2.2]crypt)]2[Bi2](NH3)4 with the known electron-deficient [Bi2]2- polyanion and a Bi=Bi double bond.

AB - From the dark-purple solution of the Zintl phase KBi in liquid ammonia dark-blue crystals of the ammonia solvate K6[Bi4](NH 3)8 were obtained. In contrast to known Bin polyanions the chemical bond in the anion [Bi4]6- is in accordance with the (8-N) rule featuring solely Bi-Bi single bonds. [Bi 4]6- is a butane-analog valence compound, and with 6 negative charges per 4 atoms it is the anion with the highest known charge per atom obtained from solution. The planarity of the trans-[Bi4] 6- unit hints at π orbital contributions of the bismuth atoms. The corresponding reactions of the phases K5Bi4 and K 3Bi2 in liquid ammonia in the presence of [2.2.2]crypt(4, 7, 13, 16, 21, 24-hexaoxa-1, 10-diazabicyclo-[8.8.8]hexacosane) lead to the salt [K([2.2.2]crypt)]2[Bi2](NH3)4 with the known electron-deficient [Bi2]2- polyanion and a Bi=Bi double bond.

KW - Bismuth

KW - Crystal structure

KW - Zintl ion

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DO - 10.1002/zaac.201300464

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JO - Zeitschrift fur Anorganische und Allgemeine Chemie

JF - Zeitschrift fur Anorganische und Allgemeine Chemie

IS - 1

ER -

^6-- the zintl anion with the highest charge per atom obtained from solution

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Keywords

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